CN102453501A - Hydrocarbon oil conversion method - Google Patents
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- CN102453501A CN102453501A CN2010105192809A CN201010519280A CN102453501A CN 102453501 A CN102453501 A CN 102453501A CN 2010105192809 A CN2010105192809 A CN 2010105192809A CN 201010519280 A CN201010519280 A CN 201010519280A CN 102453501 A CN102453501 A CN 102453501A
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Abstract
The invention relates to a hydrocarbon oil conversion method, which comprises the following steps that: the hydrocarbon oil is subjected to thermal cracking in a lift pipe reaction vessel under the partial thermal cracking condition, and in addition, products generated by the partial thermal cracking and catalytic cracking catalyst particles take contact reaction under the catalytic pyrolysis condition. After the method is adopted, the yield of ethylene during low-carbon olefin preparation from the hydrocarbon oil, particularly from the heavy oil can be effectively improved, and simultaneously, the yield of propylene can be ensured not to be reduced but even higher.
Description
Technical field
The present invention relates to a kind of conversion method for hydrocarbon oil.
Background technology
Ethene and propylene are important chemical material, to the very vigorous and continuous growth of its demand.Ethene, the propylene of existing market more than 95% produced the low-carbon alkene technology by naphtha steam cracking and heavy-oil catalytic and provided.Heavy-oil catalytic is produced the low-carbon alkene operator and is utilized catalytic pyrolysis technology, and energy consumption is low, and ingredient requirement is low, and the product profile adjustment is flexible, has bigger development prospect satisfying on the ever-increasing demand in future market.
Riser reactor has that the unit volume treatment capacity is big, gas-solid contact efficiency advantages of higher and widespread use.In the riser catalytic cracking reaction process, the hydrocarbon ils after the preheating contacts, vaporizes and react with high temperature catalyst from revivifier after nozzle gets into reactor drum, and the reaction times is greatly about 3 seconds.But because the contrary gravity field of gas-solid and stream flows; Exist the bigger diameter of axle to the mobile ununiformity in the riser tube, the gas-solid back-mixing is big, residence time skewness etc.; And because the sedimentation of coke that generates in the reaction process on catalyst surface and active site, sharply descends activity of such catalysts.Research shows that the catalyst activity in riser tube exit has only about 1/3 of initial activity at present, and reaction was carried out about 1 second, and activity of such catalysts descends about 50%.Like this, sharply descend in the second half section of riser reactor activity of such catalysts, katalysis greatly weakens, and heat cracking reaction increases, and produces more dry gas and increases content of olefin in gasoline.
Catalytic cracking reaction is the reaction system of a complicacy, is a parallel consecutive reaction process on the whole.Main reaction has reactions such as cracking, cyclisation, isomerizing, aromizing, hydrogen transference, alkylation, condensation.These several kinds reactions all are the important reactions in the catalytic cracking process, but their reaction conditions is a contradiction.For addressing this problem, software engineering researchers invent many relevant art solve, such as ending agent technology, two-stage riser technological (CN1118539C), series connection riser tube technology MIP (CN1237477A), technological (CN1069054A) technology of double lifting leg etc.CN1237477A has proposed catalyst cracker is divided into the notion of two reaction zones, and has developed corresponding riser reactor.Its main thought is the first reaction zone riser tube with the cracking reaction that generates alkene is main, generates second reaction zone that the intermediate product that is rich in alkene gets into hole enlargement again and carries out secondary reaction.The reaction of second reaction zone mainly comprises the cracking of isomerizing, hydrogen transference and appropriateness, reaches the purpose that reduces gasoline olefin and increased low carbon olefine output.
In addition, raw material becomes gradually and heavily becomes bad in recent years, and the refinery requires to improve the ability of catalyzer pressure fuel, improves the particularly productive rate of ethene of low-carbon alkene, and is therefore, also harsh more to the requirement of its supporting catalyzer.
What heavy oil catalytic pyrolysis produced that the process of ethene pursues is some intermediates in a series of consecutives and the parallel reactor; Belong to irreversible multiple reaction network; There are competition in thermal response and catalyzed reaction on reaction times and level of response, finally can generate such as coke, methane, H
2Etc. non-title product, side reaction is many, and inactivation is fast.Compare with DCC with FCC; The catalytic thermal cracking catalyst primary first-order equation is different with the secondary reaction type; Need the side reaction of inhibition also different, degree and selectivity how to control thermal response and catalyzed reaction are most important, and catalyzer should fully take into account the balance of these two types of reactions in the preparation process.
For example, CN1031029A discloses a kind of cracking catalyst of clay molecular sieve with layer structure.Preparing the used sodium type laminated clay of this catalyzer is with sodium chloride aqueous solution and the exchange of natural calcium type soil, makes through filtration, drip washing; Or mix in water with highly acid polystyrene sodium type Zeo-karb and natural calcium type soil and to stir exchange 8 hours, hold over night gets that upper strata particles suspended diameter processes less than 2 microns clay.Though using the little anti-initial activity of light oil of this catalyzer of calcium type laminated clay preparation is 46%, the catalytic cracking light oil microactivity after 800 ℃ of water vapor deactivations are handled 4 hours has only 28%, can not satisfy the requirement of industry to catalyst stability.
And for example; CN1031489A discloses a kind of complex carrier or Preparation of catalysts method that contains clay molecular sieve with layer structure; Be each component raw material with this complex carrier or catalyzer: the laminated clay of montomorillonite class or regular interbed mineral structure, zeolite molecular sieve, refractory oxide, clay are by required mixed moulding; Carry out crosslinking reaction with linking agent then, and steps such as warp is aging, roasting are processed required carrier or catalyzer.
For another example, CN1211470A points out that the catalytic pyrolysis catalyst for making ethylene need increase uncle's carbonium ion and generate and directly cracking, suppresses isomery.This method adopts modified molecular screen increases such as alkaline earth metals calcium, magnesium to select the shaped reaction performance.But catalyst activity is still on the low side, must strengthen the catalyzer usage quantity in the production, strengthens the agent consumption, could keep required activity of such catalysts requirement.
Summary of the invention
The object of the present invention is to provide that a kind of new heavy oil cracking ability is strong, the low-carbon olefines high-output conversion method for hydrocarbon oil of ethene particularly.
The invention provides a kind of conversion method for hydrocarbon oil, wherein, this method is included in and makes under the hydrocarbon ils generation portion of hot cracked condition; In riser reactor; Make the hydrocarbon ils thermo-cracking, and under the catalytic pyrolysis condition, portion of hot cracked product and catalyst cracking particles contact reacts will take place.
Adopt method of the present invention can effectively improve the particularly productive rate of the ethene of heavy oil producing light olefins of hydrocarbon ils, the productive rate that can guarantee simultaneously propylene does not reduce even is higher.For example, according to a kind of embodiment of the present invention, be provided with catalyst feeds, hydrocarbon oil feed mouth at riser reactor; Said riser reactor also comprises sleeve pipe, and said telescopic one end is communicated with the hydrocarbon oil feed mouth, and the other end is positioned at riser reactor; And the position of the telescopic the other end is higher than the position of catalyst feeds; Catalyzer in the entering riser reactor, is carried hydrocarbon ils from the hydrocarbon ils nozzle under the castering action that promotes medium in advance, owing to form inertia area in the sleeve pipe in sleeve pipe; And make hydrocarbon ils temporarily not reach catalyzer; And catalyzer process around the sleeve pipe touches hydrocarbon ils then, and the finish that carries out catalyzed reaction and routine again separates, catalyst regeneration process.Thermo-cracking takes place in said hydrocarbon ils in sleeve pipe under the thermo-cracking condition, portion of hot cracked product then will take place contact with catalyzer and proceed catalytic cracking reaction, thereby improve the productive rate of ethene.In addition, under the preferable case, adopt the supporting catalyzer of conversion method for hydrocarbon oil provided by the invention, can further improve the productive rate of ethene and propylene.
Description of drawings
Fig. 1 is the synoptic diagram of riser reactor used in the method for the present invention.
Embodiment
According to conversion method for hydrocarbon oil provided by the invention; Said method is included in and makes under the hydrocarbon ils generation portion of hot cracked condition, in riser reactor, makes the hydrocarbon ils thermo-cracking; And under the catalytic pyrolysis condition, portion of hot cracked product and catalyst cracking particles contact reacts will take place.
According to method of the present invention; Make under the hydrocarbon ils generation portion of hot cracked condition as long as can be implemented in; In riser reactor; Make the hydrocarbon ils thermo-cracking, and portion of hot cracked product will take place under the catalytic pyrolysis condition and the catalytic variety of way of catalyst cracking particles all is applicable to the present invention.
According to method of the present invention; Said riser reactor is provided with catalyst feeds and hydrocarbon oil feed mouth; Said riser reactor also comprises sleeve pipe, and said telescopic one end is communicated with the hydrocarbon oil feed mouth, and the other end is positioned at riser reactor; And the position of the telescopic the other end is higher than the position of catalyst feeds, thereby makes catalyst cracking particles not get in the sleeve pipe.According to of the present invention a kind of concrete preferred embodiment, said conversion method for hydrocarbon oil comprises sends into riser reactor through catalyst feeds and hydrocarbon oil feed mouth respectively with catalytic cracking catalyst and hydrocarbon ils; In said sleeve pipe, under generation portion of hot cracked condition, make the hydrocarbon ils thermo-cracking, and on the telescopic the other end, under the catalytic pyrolysis condition, portion of hot cracked product and catalyst cracking particles contact reacts will take place.Catalytic cracking catalyst and hydrocarbon ils got into through catalyst feeds and hydrocarbon oil feed mouth respectively can carry out simultaneously in the riser reactor also can proceed step by step; As long as guarantee in the sleeve pipe of said riser reactor; Taking place to make the hydrocarbon ils thermo-cracking under the portion of hot cracked condition, and on the telescopic the other end; Under the catalytic pyrolysis condition, portion of hot cracked product will take place and the catalyst cracking particles contact reacts gets final product.
Under the preferable case; In order to guarantee in sleeve pipe, taking place to make the hydrocarbon ils thermo-cracking under the portion of hot cracked condition; Then under the catalytic pyrolysis condition; Portion of hot cracked product and catalyzer contact reacts will take place, and said telescopic height is the 1/7-1/2 of riser reactor total height, more preferably 1/6-1/3.
According to the present invention, said riser reactor can be selected from the equal diameter riser tube, etc. in linear speed riser tube and the various change diameter riser tube any one.
The present invention is to the shape and the not special qualification of the telescopic shape in the said riser reactor of said riser reactor main body, and generally speaking, said riser reactor main body and sleeve pipe all can be right cylinder.The selectable range of said riser reactor main body and telescopic pipe diameter is broad also; For be beneficial to of the present invention make hydrocarbon ils take place under the portion of hot cracking condition reaction and under the catalytic pyrolysis condition; The catalytic coordination that portion of hot cracked product and catalyzer take place is carried out; From the consideration of optimizing reaction efficiency, said telescopic pipe diameter can be the 1/3-1/2 of the pipe diameter of riser reactor main body.Said sleeve pipe can be positioned at any side near riser reactor main body tube wall; Also can be in the central zone between the two side of riser reactor main body; From the consideration of optimizing reaction efficiency; The central zone of said sleeve pipe between the two side of riser reactor main body, as, said sleeve pipe can with the coaxial setting of riser tube.
Said hydrocarbon oil feed mouth is communicated with telescopic one end, and hydrocarbon ils is got in the sleeve pipe, and said hydrocarbon oil feed mouth can be positioned on sleeve pipe sidewall or the diapire.The quantity of its opening for feed also can be according to the needs of the inlet amount of hydrocarbon ils and suitably increase and decrease for example, can be 1-3.In order to make hydrocarbon ils in said sleeve pipe, better carry out described portion of hot scission reaction, preferred sleeve pipe height (preferably with identical from the height of hydrocarbon oil feed mouth to discharge port) is the 1/7-1/2 of riser tube total height, more preferably 1/6-1/3.
According to the present invention, in order to be beneficial to the hydrocarbon ils in the sleeve pipe to be heated, the position of the said telescopic the other end is higher than the position of catalyst feeds; Under the preferable case; The position of said hydrocarbon oil feed mouth is higher than the position of catalyst feeds, for example, and for highly being the riser reactor of 25-35 rice; The position of said hydrocarbon oil feed mouth can be higher than the position 5-10 rice of catalyst feeds, more preferably 6-8 rice.Under the preferable case, promote in order to make catalyzer in riser reactor, be raised homogeneous media, said catalyst feeds can be the 1/6-1/3 of riser reactor height to the distance of riser reactor bottom.
Under the preferable case, in riser reactor, promote operation in order to make catalytic cracking catalyst, said riser reactor can also be provided with preparatory lifting medium inlet, and said preparatory lifting medium inlet generally is positioned at the bottom of riser reactor.Said preparatory lifting medium can be dry gas, steam or their mixture.
Above-mentioned riser reactor can be through setting up a sleeve pipe in existing riser reactor, and telescopic one end is communicated with the hydrocarbon oil feed mouth of riser reactor, and the conversion zone that the telescopic the other end is positioned at riser reactor gets final product.As long as can satisfying to make, said telescopic size taking place under the portion of hot cracked condition; Make hydrocarbon ils thermo-cracking in sleeve pipe; And the reaction times of preferably satisfying the thermo-cracking in sleeve pipe get final product, as long as the size of said riser reactor equally also satisfies on the telescopic the other end, under the catalytic pyrolysis condition; Portion of hot cracked product and catalyst cracking particles contact reacts will take place, and get final product the reaction times of preferably satisfying catalytic cracking.Generally, the height of said riser reactor generally can be 5-100 rice, is preferably 10-90 rice; Caliber can be 0.01-3 rice, is preferably 0.1-1.5 rice.
Wherein, Make hydrocarbon ils generation portion of hot cracked condition can comprise the time of the temperature and the thermo-cracking of thermo-cracking; The selectable range broad of the temperature of said thermo-cracking, for fear of the problem of too high issuable catalyst member inactivation of temperature or structural breakdown, temperature is crossed the low lower problem of issuable thermal response degree; The temperature of said thermo-cracking can be 500-700 ℃, is preferably 550-650 ℃; The selectable range broad of the time of said thermo-cracking; Problem for fear of the issuable product distribution of the overlong time of thermo-cracking variation; The time of thermo-cracking is too short possibly to produce raw oil thermal response problem not too fully; Under the preferable case, the time of said thermo-cracking can be 0.01-1.5 second, is preferably 0.05-1 second.
According to the present invention, the condition of said catalytic pyrolysis can comprise temperature of reaction and reaction times, the selectable range broad of the temperature of said catalytic pyrolysis, and said temperature of reaction can be 500-700 ℃, is preferably 550-700 ℃; The reaction times of catalytic pyrolysis can be 1-5 second, is preferably 2-4 second.
According to the present invention; The consumption of said catalytic cracking catalyst can for known in those skilled in the art can be under the catalytic pyrolysis condition; The catalytic conventional amount used of portion of hot cracked product and catalyzer will take place, under the preferable case, from taking all factors into consideration of cost and the productive rate that further improves ethene and propylene; The weight ratio of said catalyst cracking particles and hydrocarbon ils can be 3-30: 1, and 6-20 more preferably: 1.
According to the present invention; Said catalytic cracking catalyst can be that the various hydrocarbon oil conversion that are applicable to are the various catalytic cracking catalysts of low-carbon alkene technology; Under the preferable case; Said catalyst cracking particles contains particle a and particle b, and said particle a contains zeolite, y-type zeolite, clay and the heat-resistant inorganic oxide matrix of MFI structure, and said particle b contains rectorite and heat-resistant inorganic oxide matrix.
According to the present invention; The selectable range broad of the weight ratio of said particle a and particle b; Generally speaking, can be according to the demand flexible particle a of catalytic cracking reaction and the weight ratio of particle b, in order to obtain better catalytic cracking effect; The weight ratio of said particle a and particle b can be 0.5-15: 1, be preferably 1-10: 1.
According to the present invention, can also contain rare earth compound in the said catalyzer, for example, can contain rare earth compound among said particle a and/or the particle b.The content of said rare earth compound can be the content of the rare earth compound that this area is conventional, under the preferable case, is benchmark with the gross weight of catalyzer, with RE
2O
3Meter, the consumption of said rare earth compound makes the content of catalyzer middle-weight rare earths oxide compound be no more than 8 weight %.Said rare earth compound can be introduced (the for example method of dipping) through existing variety of way, as long as make catalyzer of the present invention contain rare earth oxide.
According to the present invention; The said particle a that contains the molecular sieve active component can be the various particles that contain the molecular sieve active component; Under the preferable case, the said preparation method who contains the particle a of molecular sieve active component comprises that the zeolite with the MFI structure contacts with the mixing of organic amine solution; The mixture that obtains and y-type zeolite mixed contact, isolate solid in the mixture and dry, solid that drying is obtained and clay and silicon sol are pulled an oar, with slurry dried that obtains and roasting.
Contain in the particulate method of molecular sieve active component in preparation of the present invention, owing in building-up process, introduced organic amine, thus make the particle that contains the molecular sieve active component of the present invention have advantages such as higher activity, heat and hydrothermal stability.Therefore; Make that heavy oil cracking ability by particle a that contains the molecular sieve active component provided by the invention and the catalyzer of the particle b that contains clay and heat-resistant inorganic oxide matrix is strong, the high raw oil of blending ratio is had heavy oil conversion performance preferably, make the particularly productive rate height of ethene of low-carbon olefines high-output.And catalyzer of the present invention is owing to contain the said particle a that contains the molecular sieve active component, and the type and the degree of primary first-order equation and the secondary reaction of the catalytic cracking catalyst that obtains when fcc raw material oil reacts are also controlled.
Although need only the particle that can obtain to contain the molecular sieve active component according to method of the present invention; But contriver of the present invention finds; When the mol ratio of the zeolite of said organic amine and MFI structure is 0.2-7: 1, be preferably 0.2-5: 1, the mol ratio of the zeolite of said y-type zeolite and MFI structure is 0.01-1: 1; Be preferably 0.1-0.75: 1, the particle that contains the molecular sieve active component that is synthesized has outstanding advantages such as catalytic activity is higher, performance is more stable.
The present invention does not limit the concentration of said organic amine solution is special, as long as guarantee to make the organic amine in the solution of organic amine to contact with the zeolite with MFI structure.Under the preferable case, more effective with contacting of the zeolite with MFI structure in order to make organic amine, the concentration of said organic amine solution is generally 0.05-15 weight %, is preferably 0.1-10 weight %.Under the preferable case, the weight ratio of the zeolite of the said MFI of having structure and organic amine solution is 1-60: 100, and 5-30 more preferably: 100.In addition, preferred y-type zeolite and the gross weight with zeolite of MFI structure are no more than 60 weight % of the weight of organic amine solution.
According to the present invention, the kind of said organic amine can be various organic amines known in the field, for example, can be selected from polyvinylamine, polymine and N, one or more in the N-dimethyl alkylamine.Wherein, the number-average molecular weight of said polyvinylamine can be 1000-10000, is preferably 1000-5000, further is preferably 1000-3000; The number-average molecular weight of said polymine can be 1000-10000, is preferably 1000-5000, further is preferably 1000-3000.To said N, the carbonatoms of the alkyl in the N-dimethyl alkylamine is not special to be limited, and can be the straight or branched alkyl of 1-15 for carbonatoms generally, for example; N, N-dimethyl-methylamine, N, N-dimethyl amine, N, N-dimethyl n propylamine, N; N-dimethyl butylamine, N, N-dimethyl-NSC 32389, N, N-dimethylhexylamine, N, N-dimethyl-octylame, N; N-dimethyl-nonyl amine, N, N-dimethyl-decyl amine, N, N-dimethyl-undecyl amine, N; N-dimethyl-lauryl amine, N, N-dimethyl-tetradecylamine and N, at least a in the N-dimethyl-pentadecyl amine.The solvent that forms organic amine aqueous solution also can be preferably water for the solvent of various routines known in the field.
According to the present invention, the zeolite that will have a MFI structure and organic amine solution mix the condition that contact and generally comprise the time that the temperature of mixing contact contacts with mixing.The temperature of said mixing contact can be selected in awide temperature range; For example, the zeolite of the said MFI of having structure mixes the temperature that contacts with organic amine solution can be 20-80 ℃, is preferably 40-70 ℃; Mix the further raising of the feasible particulate performance that contains the molecular sieve active component that makes of prolongation of duration of contact; But mixing long increase rate to their performances duration of contact is also not obvious, therefore, and generally speaking; The said contact blended time can be 30-60 minute, is preferably 35-50 minute.
The present invention mixes the not special qualification of the mode that contacts to the mixture that obtains with y-type zeolite, contact as long as the mixture that obtains is mixed with y-type zeolite, but contriver of the present invention finds; Y-type zeolite is joined in the said mixture in batches; The resultant particle that contains the molecular sieve active component has better ethylene selectivity, has better heavy oil conversion performance, so the present invention preferably joins y-type zeolite in the said mixture in batches; Under the preferable case; The add-on of every batch of y-type zeolite is at most 80 weight % of the total consumption of y-type zeolite, is preferably 30-70 weight %, also comprises the timed interval between the step of adjacent two batch mixing; The said timed interval can be 5-120 minute, is preferably 15-60 minute.
According to the present invention; The zeolite of the said MFI of having structure can be various zeolites with MFI structure known in those skilled in the art; Be preferably HZSM-5 zeolite and/or element modified ZSM zeolite, for example, one or more in the ZSM-5 zeolite of the ZSM-5 zeolite of phosphorus modification, phosphorus and rare earth modified ZSM-5, phosphorus and iron modification, in the ZSP zeolite of the ZRP zeolite of phosphorus modification and phosphorus modification; Under the further preferable case, said silica alumina ratio (SiO with zeolite of MFI structure
2/ Al
2O
3) being preferably 15-300, silica alumina ratio especially is preferably 30-200.
According to the present invention, said y-type zeolite can be for well known to a person skilled in the art various y-type zeolites, for example, can be selected from REY, REHY, USY, HY, REUSY, PREY, the PREHY zeolite one or more.
Among the present invention; The method of the solid that obtains and clay and silicon sol making beating can be the methods of beating of routine known in the field, therefore, the weight ratio of the mixture of the said solid that obtains and clay and silicon sol not had particular requirement; Generally speaking; The weight ratio of the mixture of solid that obtains and clay and silicon sol can be 1: 0.2-10 is preferably 1: 0.5-6, and the solid content of gained mixture is 3-40 weight % after mixing usually.
The selectable range broad of the weight ratio of said clay and silicon sol, but under the preferable case, the weight ratio of said clay and silicon sol can be 0.01-10: 1, further be preferably 0.1-4: 1.
Wherein, the weight of said clay is in its butt weight, and the weight of said silicon sol is with SiO
2Meter.
Said silicon sol can be purchased acquisition and also can prepare according to method known in those skilled in the art for this area silicon sol commonly used.
Under the preferable case, the step of the solid that obtains and clay and silicon sol making beating can also be comprised the adding rare earth compound, be benchmark with the particulate gross weight that contains the molecular sieve active component that obtains, with RE
2O
3Meter, the consumption of said rare earth compound makes the said content that contains the particle middle-weight rare earths oxide compound of molecular sieve active component be no more than 8 weight %.Wherein, RE representes REE.
Wherein, said clay can this area conventional various clays, for example, can be selected from rectorite, kaolin, polynite, zeyssatite, halloysite, saponite, sepiolite, attapulgite, hydrotalcite and the wilkinite one or more.
Said rare earth compound can be the conventional various rare earth compounds in this area; For example; Can be in muriate, bromide and the nitrate salt of rare earth one or more; In addition, can be a kind of salt of REE, also can be the mixed rare earth compound that comprises multiple REE commonly used in the catalyst preparation process.Said REE is preferably selected from one or more in the lanthanon.Said rare earth compound can add with solid form or with the form of the aqueous solution of rare earth compound, and the concentration of the aqueous solution of said rare earth compound generally can be 20-60 weight %.
According to the present invention; Said exsiccant method can adopt the drying means of various routines known in the field; Its operational condition also can be carried out according to condition known in those skilled in the art, for example, and one or more in seasoning, vacuum-drying and the spraying drying; Be preferably spraying drying, said exsiccant condition generally comprises the exsiccant temperature can be 100-200 ℃, and the exsiccant time can 1-10 hour.
The method of said roasting can adopt the method for various routines known in the field, and its operational condition also can be carried out according to condition known in those skilled in the art, as long as organic amine is removed.For example, the temperature of roasting can be 400-650 ℃, and the time of roasting can be 0.5-6 hour.
According to a kind of embodiment that has of the present invention, said combination of molecular sieve and the particulate preparation method who contains the molecular sieve active component comprise following concrete steps:
(1) zeolite with the MFI structure mixes with organic amine solution (mass percent concentration is 0.05-15 weight %), stirs 30-60 minute;
(2) divide the many batches of mixtures that obtain with step (1) to mix y-type zeolite, the add-on of every batch of y-type zeolite is at most 80 weight % of the total consumption of y-type zeolite, is preferably 30-70 weight %, and the timed interval is 5-120 minute, and stirs 60-120 minute;
(3) combination of molecular sieve that step (2) is obtained filters, dries, obtains solid;
(4) preparation pH value is the silicon sol of 1-3, and the preparation method of said silicon sol can prepare according to ordinary method, for example, and can be with water glass solution (SiO
2Concentration is preferably 15-40 weight %), modulus of water glass is 3-3.5) join in the sulfuric acid (the preferred mass percentage concentration is 15-50%), add soon earlier, and stir, add half back and slowly add, and stop to stir, the maintenance slurry pH value is 1-3;
(5) clay is mixed with the silicon sol that step (4) obtains, obtain containing clay and silicon sol mixture (weight ratio of clay and silicon sol is 0.1-10: 1, the weight of clay is in its butt weight, the weight of silicon sol is with SiO
2Meter);
(6) solid that step (3) is obtained mixes with the mixture of silicon sol with the clay that step (5) obtains that (weight ratio of the solid that step (3) obtains and the mixture of clay and silicon sol is 1: 0.2-10; And the solid content that mixes back gained mixture usually is 3-40 weight %); Stir spray drying forming, roasting.
Under the optimum condition, among the said particle b, the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.
According to the present invention, the kind of said heat-resistant inorganic oxide matrix can adopt this area heat-resistant inorganic oxide matrix commonly used.For example, said heat-resistant inorganic oxide matrix can be selected from one or more in silicon oxide, gama-alumina, Natural manganese dioxide, silica-alumina and the aluminum oxide-phosphorus oxide, is preferably silicon oxide.
Said rectorite is preferably basal spacing d
001Value be 2.7-5.0nm, the BET specific surface area is 100-300m
2The rectorite of/g.
According to the present invention, under the preferable case, said heat-resistant inorganic oxide matrix contains silicon-dioxide, and the preparation method of said particle b comprises: sulfuric acid is mixed with water glass, obtain the slurries of pH value for 1-3, rectorite is mixed with the slurries that obtain, dry and roasting.
The adjustable extent broad of said rectorite and the weight ratio of the slurries that obtain; Contain rectorite and heat-resistant inorganic oxide matrix as long as guarantee among the said particle b; And preferably make the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.Therefore, generally speaking, said rectorite can be 1 with the weight ratio of the slurries that obtain: 1.5-50.
The method and the condition of said drying, roasting detail in preamble, repeat no more at this.
Under the preferable case, in the process of preparation particle b, introduce rare earth compound (being that particle b contains rare earth compound), specifically, can before drying, rectorite be mixed with rare earth compound with the mixture of the slurries that obtain.Gross weight with catalyzer is a benchmark, with RE
2O
3Meter, the consumption of said rare earth compound makes the content of catalyzer middle-weight rare earths oxide compound be no more than 8 weight %.
Except providing according to method of the present invention particle a and the particle b, catalyzer of the present invention can be after with particle a that makes respectively and particle b moulding, with 0.5-15: 1, be preferably 1-10: 1 weight ratio mixes and can make.
Be example with isometrical riser reactor below, a kind of embodiment of method provided by the present invention further explained in conjunction with accompanying drawing, the reactor drum that all the other are various can to realize method of the present invention similarly, the present invention repeats no more.
As shown in Figure 1, hydrocarbon ils carries the sleeve pipe 4 that is got into riser reactor by the hydrocarbon oil feed mouth that is positioned at the sleeve pipe sidewall through pipeline 3 by thinner (for example atomized water steam), is taking place to make the hydrocarbon ils thermo-cracking under the portion of hot cracked condition; Promoting medium in advance gets into through the bottom feed mouth of pipeline 1 by riser reactor 2; Catalytic cracking catalyst from pipeline 5 is promoting under the castering action of medium in advance; Move upward along riser tube, the generation portion of hot cracked product of discharging with sleeve pipe 4 mixes in riser tube and is incorporated in contact reacts under the catalytic cracking condition.Wherein, The catalytic cracking catalyst that is carried by preparatory lifting medium is passed in the riser reactor through pipeline 5; And can simultaneously the hydrocarbon ils that is carried by thinner (like atomizing steam) be fed in the sleeve pipe through pipeline 3; The catalytic cracking catalyst that carries by preparatory lifting medium and by thinner (like atomizing steam) as long as the feeding of the hydrocarbon ils that carries and guarantee in the sleeve pipe of riser reactor along moving upward of pipe makes hydrocarbon ils heat that the portion of hot cracking take place, and on the telescopic the other end; Under the catalytic pyrolysis condition, portion of hot cracked product will take place and the catalyst cracking particles contact reacts gets final product.
Following preparation embodiment and embodiment will further explain the present invention, but therefore not limit the present invention.
In each embodiment and Comparative Examples, Na in the zeolite
2O, Fe
2O
3, NiO, Al
2O
3, SiO
2The content mensuration that adopts x-ray fluorescence method mensuration, micro-activity and abrasion index (AI) referring to [Science Press, nineteen ninety publishes for " petrochemical complex analytical procedure " (RIPP experimental technique), volumes such as Yang Cuiding].
800 ℃/4h active (MA) is defined as: 800 ℃ of activity datas of being surveyed after 4 hours with 100% steam aging down, MA method are measured referring to [" petrochemical complex analytical procedure " (RIPP experimental technique), volumes such as Yang Cuiding, Science Press, nineteen ninety publication].
The composition of used hydrocarbon ils is as shown in table 1 among the embodiment.
Preparation embodiment 1
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
A: preparation combination of molecular sieve and particle a
(1) under 30 ℃; With 14kg ZSP-3 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product; ZSP-3 silica alumina ratio=40), mix with the 100kg polyvinylamine aqueous solution (number-average molecular weight of polyvinylamine is 1800 (available from westernization appearance (Beijing) Science and Technology Ltd.s), and the mass percent concentration of the polyvinylamine aqueous solution is 3%); Stirred 40 minutes, and obtained slurries 114kg;
(2) under 40 ℃, 4kg DASY2.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product, silica alumina ratio is 5.6) is mixed with the slurries that step (1) obtains, stir and obtained slurries 118kg in 40 minutes;
(3) under 40 ℃, again 4kg DASY2.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product, silica alumina ratio is 5.6) is mixed with the slurries that step (2) obtains, stir and obtained slurries 122kg in 20 minutes, obtain combination of molecular sieve;
(4) combination of molecular sieve that step (3) is obtained filters, and dries 5 hours down in 120 ℃, obtains solid 22.2kg;
(5) preparation of silicon sol: with 20kg decationized Y sieve water and 35kg water glass (SiO
2Content 28.4 weight %, modulus of water glass 3.1) mix, join the H of 30kg
2SO
4In the solution (mass percent concentration is 30 weight %), the speed of adding is 60kg/ hour, and the silicon sol slurries 85kg that stirring obtains pH=1.6 is (with SiO
2Meter, silicon sol is 9.9kg);
(6) 19kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) is mixed with the slurries that step (5) obtains, stirred 30 minutes, obtain the mixture 104kg (solid content of mixture is 22.7 weight %) of kaolin and silicon sol slurries;
(7) in the kaolin that solid that step (4) is obtained and step (6) obtain and the mixture of silicon sol slurries; Stirred 20 minutes; (drying temperature is 120 ℃ to spray drying forming; Be 3 hours time of drying), roasting (maturing temperature is 550 ℃, and roasting time is 2 hours) obtains containing the particle a of molecular sieve active component.
B: preparation particle b
(1) with 10kg decationized Y sieve water and 18kg water glass (SiO
2Content 28.4 weight %, modulus 3.1) mix, join the H of 10kg
2SO
4In the solution (mass percent concentration is 50%), the speed of adding is 60kg/ hour, stirs the slurries 38kg that obtains pH=1.6;
(2) with 15kg rectorite (Zhongxiang City, Hubei rectorite, solid content 87 weight %, basal spacing d
001Value be 4nm, specific surface area is 200m
2/ g) slurries with step (1) mix, and stirring and obtaining the pH value is 1.8 slurries, and spraying drying (drying temperature is 120 ℃, and be 3 hours time of drying) obtains particle b.
C: Preparation of Catalyst
Particle a and particle b were mixed by weight 10: 1, after the roasting (maturing temperature is 550 ℃, and roasting time is 2 hours), remove free Na with deionized water wash
+Ion, dry (drying temperature is 150 ℃, and be 2 hours time of drying) obtains catalyzer 1.
Preparation embodiment 2
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to preparing embodiment 1 prepares catalyzer; Different is; In the step of preparation particle a: (number-average molecular weight of polymine is 3000 (available from the good companies of Beijing Cohan) to change the 100kg polyvinylamine solution into 280kg polyethyleneimine: amine aqueous solution; The mass percent concentration of polyethyleneimine: amine aqueous solution is 5%), the ZSP-3 molecular sieve of 14kg is replaced by 20kg ZRP (catalyzer Shandong branch office of China Petrochemical Industry product, silica alumina ratio is 60); The consumption of DASY2.0 molecular sieve is 3kg (catalyzer Shandong branch office of a China Petrochemical Industry product; Silica alumina ratio is 4.9) (in step (2) and (3), adding 1kg and 2kg respectively), simultaneously particle a and particle b were mixed by weight 5: 1, obtain catalyzer 2.
Preparation embodiment 3
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to preparing embodiment 1 prepares catalyzer, and different is to change the 100kg polyvinylamine solution into 500kg N; N-dimethyl-dodecyl amine aqueous solution (N; N-dimethyl-lauryl amine is available from Wuhan Yuancheng Technology Development Co., Ltd.), N, the mass percent concentration of N-dimethyl-dodecyl amine aqueous solution is 10%); The ZSP-3 molecular sieve of 14kg is by HZSM-5 (catalyzer Shandong branch office of the China Petrochemical Industry product of 10kg; Silica alumina ratio is 45), the consumption of DASY2.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product, silica alumina ratio is 3.6) is 7.5kg (in step (2) and (3), adding 5kg and 2.5kg respectively); Simultaneously particle a and particle b were mixed by weight 15: 1, obtain catalyzer 3.
Preparation embodiment 4
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to preparing embodiment 1 prepares catalyzer, and different is that particle a and particle b are obtained by weight mixing in 1: 1.Obtain catalyzer 4.
Preparation embodiment 5
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to preparing embodiment 1 prepares catalyzer, and different is, with DASY2.0 molecular sieve disposable adding in step (2) of 8kg.Obtain catalyzer 5.
Preparation embodiment 6
This preparation embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to preparing embodiment 1 prepares catalyzer, and different is, in the step (2) of preparation particle b with the chlorination mixed rare earth solution of 0.4kg (with RE
2O
3The concentration of meter is 23.5 weight %, and rare earth new material ltd in Gansu produces, La in the rare earth oxide
2O
3Account for 23 weight %, CeO
2Account for 46 weight %, other rare earth oxide content is 31 weight % (other rare earth oxide comprises Praseodymium trioxide and rubidium oxide)) and rectorite join together in the slurries of step (1) of preparation particle b.Obtain catalyzer 6.
Embodiment 1
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Adopt isometrical riser reactor shown in Figure 1; Wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters; The hydrocarbon oil feed mouth is positioned at apart from riser reactor 2 bottoms on 5 meters the sidewall, and catalyst feeds is positioned at apart from riser reactor 2 bottoms on 1 meter the sidewall; The pipe diameter that is set in the sleeve pipe 4 in the riser reactor 2 is 0.6 meter; Highly be 5 meters; And with riser reactor 2 coaxial settings; And an end of sleeve pipe 4 is connected and is communicated with (position that sleeve pipe 4 is connected with the hydrocarbon oil feed mouth is apart from 0.2 meter of sleeve bottom) with the hydrocarbon oil feed mouth, and the other end of sleeve pipe 4 is the hydrocarbon ils entrance location that the position of exit end is higher than sleeve pipe 4.
Hydrocarbon ils is preheating to 300 ℃ through pipeline 3 is got into sleeve pipe 4 by the hydrocarbon oil feed mouth in; Hydrocarbon ils is at sleeve pipe 4 internal reactions; Temperature of reaction is 600 ℃; Reaction times is 1 second, and the portion of hot cracked product that obtains is got in the riser reactor 2 by the other end port of sleeve pipe 4, contacts riser reactor 2 in the catalyst cracking particles that is made by preparation embodiment 1 that is got into by catalyst feeds through pipeline 5 and up under the castering action by the preparatory lifting medium (280 ℃ of high-temperature vapors of preheating) in the pipeline 1 entering riser reactor 2; At riser reactor 2 internal reactions; Temperature of reaction is 640 ℃, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 12: 1, and the total reaction time in riser reactor 2 is 3 seconds.Reaction product in the riser reactor 2 is carried out finish separate, products therefrom is formed as shown in table 2.
Comparative Examples 1
This Comparative Examples is used to explain the method for transformation of the hydrocarbon ils of prior art.
Transform hydrocarbon ils according to the method for embodiment 1, different is, no sleeve pipe in the said reactor drum, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 1 in riser reactor contact reacts.The result is as shown in table 2.
Embodiment 2
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Adopt isometrical riser reactor shown in Figure 1; Wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters; The hydrocarbon oil feed mouth is positioned at apart from riser reactor 2 bottoms on 7 meters the sidewall, and catalyst feeds is positioned at apart from riser reactor 2 bottoms on 1 meter the sidewall; The pipe diameter that is set in the sleeve pipe 4 in the riser reactor 2 is 0.6 meter; Highly be 10 meters; And with riser reactor 2 coaxial settings; And an end of sleeve pipe 4 is connected and is communicated with (position that is connected with the hydrocarbon oil feed mouth of sleeve pipe 4 is apart from 0.5 meter of sleeve bottom) with the hydrocarbon oil feed mouth, sleeve pipe 4 the other ends are the hydrocarbon ils entrance location that the position of exit end is higher than sleeve pipe 4.
Hydrocarbon ils and preheating 300 ℃ are got in the sleeve pipe 4 by the hydrocarbon oil feed mouth through pipeline 3; Hydrocarbon ils is at sleeve pipe 4 internal reactions; Temperature of reaction is 550 ℃; Reaction times is 0.05 second, and the portion of hot cracked product that obtains is got in the riser reactor 2 by the other end port of sleeve pipe 4, contacts riser reactor 2 in the catalyst cracking particles that is made by preparation embodiment 1 that is got into by catalyst feeds through pipeline 5 and up under the castering action by the preparatory lifting medium (280 ℃ of high-temperature vapors of preheating) in the pipeline 1 entering riser reactor 2; At riser reactor 2 internal reactions; Temperature of reaction is 600 ℃, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 20: 1, and the total reaction time in riser reactor 2 is 4 seconds.Reaction product in the riser reactor 2 is carried out finish separate, products therefrom is formed as shown in table 2.
Comparative Examples 2
This Comparative Examples is used to explain the method for transformation of the hydrocarbon ils of prior art.
Transform hydrocarbon ils according to the method for embodiment 2, different is, no sleeve pipe in the said reactor drum, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 2 in riser reactor contact reacts.The result is as shown in table 2.
Embodiment 3
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Adopt isometrical riser reactor shown in Figure 1; Wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters; The hydrocarbon oil feed mouth is positioned at apart from riser reactor 2 bottoms on 6 meters the sidewall, and catalyst feeds is positioned at apart from riser reactor 2 bottoms on 1 meter the sidewall; The pipe diameter that is set in the sleeve pipe 4 in the riser reactor 2 is 0.6 meter; Highly be 6 meters; And with riser tube 2 coaxial settings; And an end of sleeve pipe 4 is connected and is communicated with (position that is connected with the hydrocarbon oil feed mouth of sleeve pipe 4 is apart from 0.3 meter of sleeve bottom) with the hydrocarbon oil feed mouth, sleeve pipe 4 the other ends are the hydrocarbon ils entrance location that the exit end position is higher than sleeve pipe 4.
Hydrocarbon ils and preheating 300 ℃ are got in the sleeve pipe 4 by the hydrocarbon oil feed mouth through pipeline 3; Hydrocarbon ils is at sleeve pipe 4 internal reactions; Temperature of reaction is 640 ℃; Reaction times is 0.08 second, and the portion of hot cracked product that obtains is got in the riser reactor 2 by the other end port of sleeve pipe 4, contacts riser reactor 2 in the catalyst cracking particles that is made by preparation embodiment 1 that is got into by catalyst feeds through pipeline 5 and up under the castering action by the preparatory lifting medium (280 ℃ of high-temperature vapors of preheating) in the pipeline 1 entering riser reactor 2; At riser reactor 2 internal reactions; Temperature of reaction is 700 ℃, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 6: 1, and the total reaction time in riser reactor 2 is 2 seconds.Reaction product in the riser reactor 2 is carried out finish separate, products therefrom is formed as shown in table 2.
Comparative Examples 3
This Comparative Examples is used to explain the method for transformation of the hydrocarbon ils of prior art.
Transform hydrocarbon ils according to the method for embodiment 3, different is, no sleeve pipe in the said reactor drum, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 3 in riser reactor contact reacts.The result is as shown in table 2.
Embodiment 4
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is the catalyzer 2 that adopts preparation embodiment 2 to make.The result is as shown in table 3.
Embodiment 5
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is the catalyzer 3 that adopts preparation embodiment 3 to make.The result is as shown in table 3.
Embodiment 6
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is the catalyzer 4 that adopts preparation embodiment 4 to make.The result is as shown in table 3.
Embodiment 7
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is the catalyzer 5 that adopts preparation embodiment 5 to make.The result is as shown in table 3.
Embodiment 8
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is the catalyzer 6 that adopts preparation embodiment 6 to make.The result is as shown in table 3.
Embodiment 9
Present embodiment is used to explain conversion method for hydrocarbon oil provided by the invention.
Method according to embodiment 1 transforms hydrocarbon ils, and different is to adopt the method that embodiment 1 provides among the CN101210187A to prepare cracking catalyst D1.The result is as shown in table 3.
Comparative Examples 4
This Comparative Examples is used to explain the method for transformation of the hydrocarbon ils of prior art.
Method according to Comparative Examples 1 transforms hydrocarbon ils, and different is to adopt the method that embodiment 1 provides among the CN101210187A to prepare cracking catalyst D1.The result is as shown in table 3.
Table 1
Table 2
Table 3
Can find out from the result of table 2 and table 3; By embodiment 1 and Comparative Examples 1, Comparative Examples 4; Embodiment 2 and Comparative Examples 2, embodiment 3 and Comparative Examples 3, and embodiment 10 can find out with the comparison of Comparative Examples 4; Method provided by the invention can effectively improve the particularly productive rate of the ethene of heavy oil producing light olefins of hydrocarbon ils, and the productive rate that can guarantee simultaneously propylene does not reduce even be higher.In addition; Through embodiment 1 can be found out with the contrast of embodiment 9, under all identical situation of other condition, adopt preferred catalytic cracking catalyst of the present invention can further improve low-carbon alkene; The productive rate of ethene particularly; And liquefied gas yield improves, and coke yield reduces, and the heavy oil productive rate reduces.
Claims (22)
1. a conversion method for hydrocarbon oil is characterized in that, this method is included in and makes under the hydrocarbon ils generation portion of hot cracked condition; In riser reactor; Make the hydrocarbon ils thermo-cracking, and under the catalytic pyrolysis condition, portion of hot cracked product and catalyst cracking particles contact reacts will take place.
2. method according to claim 1; Wherein, said riser reactor is provided with catalyst feeds, hydrocarbon oil feed mouth, and said riser reactor also comprises sleeve pipe; Said telescopic one end is communicated with the hydrocarbon oil feed mouth; The other end is positioned at riser reactor, and the position of the telescopic the other end is higher than the position of catalyst feeds, and catalyst cracking particles and hydrocarbon ils are sent into riser reactor through catalyst feeds and hydrocarbon oil feed mouth respectively; In said sleeve pipe, under generation portion of hot cracked condition, make the hydrocarbon ils thermo-cracking, and on the telescopic the other end, under the catalytic pyrolysis condition, portion of hot cracked product and catalyst cracking particles contact reacts will take place.
3. method according to claim 2, wherein, the telescopic height is the 1/7-1/2 of riser reactor total height.
4. according to any described method among the claim 1-3, wherein, make hydrocarbon ils generation portion of hot cracked condition comprise that the temperature of thermo-cracking is 500-700 ℃, the time of thermo-cracking is 0.01-1.5 second.
5. method according to claim 4 wherein, makes hydrocarbon ils generation portion of hot cracked condition comprise that the temperature of thermo-cracking is 550-650 ℃, and the time of thermo-cracking is 0.05-1 second.
6. according to any described method among the claim 1-3, wherein, the catalytic pyrolysis condition comprises that temperature of reaction is 500-700 ℃, and the catalytic time is 1-5 second, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 3-30: 1.
7. method according to claim 6, wherein, the catalytic pyrolysis condition comprises that temperature of reaction is 550-700 ℃, and the catalytic time is 1-4 second, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 6-20: 1.
8. method according to claim 1 and 2; Wherein, Said catalyst cracking particles contains particle a and particle b, and said particle a contains zeolite, y-type zeolite, clay and the heat-resistant inorganic oxide matrix of MFI structure, and said particle b contains rectorite and heat-resistant inorganic oxide matrix.
9. method according to claim 1, wherein, by weight, the ratio of said particle a and particle b is 0.5-15: 1.
10. method according to claim 9, wherein, by weight, the ratio of said particle a and particle b is 1-10: 1.
11. method according to claim 8, wherein, said particle a and/or particle b also contain rare earth compound, are benchmark with the gross weight of catalyzer, with RE
2O
3Meter, the consumption of said rare earth compound makes the content of catalyzer middle-weight rare earths oxide compound be no more than 8 weight %.
12. method according to claim 8, wherein, the preparation method of said particle a comprises that the zeolite with the MFI structure contacts with the mixing of organic amine solution; The mixture that obtains and y-type zeolite mixed contact, isolate solid in the mixture and dry, solid that drying is obtained and clay and silicon sol are pulled an oar, with slurry dried that obtains and roasting.
13. method according to claim 12, wherein, the weight ratio of the zeolite of said organic amine and MFI structure is 0.2-7: 1, and the weight ratio of the zeolite of said y-type zeolite and MFI structure is 0.01-1: 1.
14. method according to claim 13, wherein, the weight ratio of the zeolite of said organic amine and MFI structure is 0.2-5: 1, and the weight ratio of the zeolite of said y-type zeolite and MFI structure is 0.1-0.75: 1.
15. method according to claim 12, wherein, said clay is selected from one or more in kaolin, polynite, zeyssatite, halloysite, saponite, sepiolite, attapulgite, hydrotalcite and the wilkinite.
16. method according to claim 12, wherein, the concentration 0.5-15 weight % of said organic amine solution.
17. according to any described method among the claim 12-16, wherein, said organic amine is selected from polyvinylamine, polymine and N, one or more in the N-dimethyl alkylamine.
18. method according to claim 12; Wherein, the zeolite of said MFI structure mixes temperature 20-80 ℃ that contacts with organic amine solution, and the time is 30-60 minute; The mixture that obtains is mixed temperature 40-80 ℃ that contacts with y-type zeolite, and the time is 60-120 minute.
19., wherein, the mixture that obtains and y-type zeolite are mixed the method that contacts comprise y-type zeolite is joined in the said mixture in batches according to claim 12 or 18 described methods.
20. method according to claim 19, the add-on of every batch of y-type zeolite are at most 80 weight % of the total consumption of y-type zeolite, also comprise the timed interval between the step of adjacent two batch mixing, the said timed interval is 5-120 minute.
21. method according to claim 8, wherein, said heat-resistant inorganic oxide matrix contains silicon-dioxide; The preparation method of said particle b comprises sulfuric acid is mixed with water glass; Obtain the slurries of pH value, rectorite is mixed contacting with the slurries that obtain, dry and roasting for 1.5-3.
22. according to the described method of claim 21, wherein, the basal spacing d of said rectorite
001Value be 2.7-5.0nm, the BET specific surface area is 100-300m
2/ g.
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